CN104203887B - The manufacture method of triphen phenols - Google Patents

The manufacture method of triphen phenols Download PDF

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CN104203887B
CN104203887B CN201380016486.1A CN201380016486A CN104203887B CN 104203887 B CN104203887 B CN 104203887B CN 201380016486 A CN201380016486 A CN 201380016486A CN 104203887 B CN104203887 B CN 104203887B
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manufacture method
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CN104203887A (en
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芦田仁
芦田一仁
桥本祐树
山本智也
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Honshu Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones

Abstract

The present invention provides to obtain 1 with single step reaction industrialization, 1,3 three (hydroxy phenyl) cycloalkane, and the method that the phenol making 2 cycloolefin 1 ketones that following formula (1) represents or 3 hydroxyl cycloalkane 1 ketones that following formula (2) represents and following formula (3) represent carries out reacting in the presence of a catalyst.In formula, R1Represent hydrogen atom, alkyl, alkoxyl, aryl radical or halogen atom, R2Representing alkyl, alkoxyl, aryl radical or halogen atom, m represents the integer of 0～2, has multiple R in whole ring2When replacing, R2Can the most identical can also be different, n represents the integer of 1～9,In formula, R1、R2, m and n and described R1、R2, m and n identical,In formula, R3Represent alkyl, alkoxyl, aryl radical or halogen atom, when a is more than 2, R3Can the most identical can also be different, a represents the integer of 0～4, and b represents the integer of 1 or 2, but, 1 a+b 5,In formula, R1、R2、R3, a, b, m and n and described R1、R2、R3, a, b, m and n identical.

Description

The manufacture method of triphen phenols
Technical field
The present invention relates to the manufacture method of triphen phenols.More particularly it relates to manufacture 1,1,3-tri-(hydroxy benzenes Base) method of cycloalkane, it is characterised in that make 2-cycloolefin-1-ketone or 3-hydroxyl cycloalkane-1-ketone and phenol exist React in the presence of catalyst.
Background technology
In the past, as the manufacture method of the triphen phenols of skeleton centered by cycloalkane, the most known employing is reacted as follows, By making phenol react in the presence of acidic with by the ketone of hydroxy phenyl substituted cycloalkane skeleton, and make The carbon atom of the carbonyl forming cycloalkane skeleton is replaced (patent documentation 1) by 2 hydroxy phenyls.
But, in the method, though to the preparation method of raw material without any record in patent documentation 1, but above-mentioned as raw material In ketone, the 3-position of cyclanone combines the difficult compound manufactured in industrialization of ring-type ketone of hydroxy phenyl.Such as, as Tetrahedron, 55 (1999), described in 6657, this kind of ketone is to use the palladium compound of high price, phosphorus compound to obtain Material, additionally, at Journal of Organic Chemistry, 56 (1991), in the method for 2853, synthesis procedure is long, Journal of Chemical Research, in the method for Synopses 366 (1995), though being reacted 1 by ring-type beta-unsaturated ketone Secondary and generate, but yield is low and required silver compound is the most non-on a small quantity, thus the method not manufactured by applicable industrialization and Obtain.
Furthermore it is known that by alkylphenol and α, alpha, beta-unsaturated ketone reacts, available α, the benzene on β-unsaturated bond The addition product (non-patent literature 1) of phenol.But, do not record in the reaction, carbonyl and the reaction of phenol and the life of trisphenol Become.
It addition, as additive method, it is also known that the method being manufactured triphen phenols by α, beta-unsaturated aldehyde and phenol, but not It it is the method (patent documentation 2 and patent documentation 3) using ketone.
And on the other hand, it is also known that hydroxyl substituted cyclic ketone and phenol carry out reacting and obtaining biphenol (patent documentation 4, patent documentation 5), but in this kind of reaction, hydroxyl is not involved in reaction, in hydroxyl replaces the ketone reaction with phenol, with Toward the generation only knowing biphenol.
Generally, when making ketone and phenol react, and when reacting with aldehydes compared with, in most cases react speed Degree, yield etc. are the lowest, because the substituent group of phenol is different, can not get goal object sometimes or yield is extremely low.
As it has been described above, replaced ketone by α, beta-unsaturated ketone or hydroxyl to manufacture triphen phenols with phenol with a step in the past Method also belong to unknown.
Prior art literature
Patent documentation
Patent documentation 1 Japanese Unexamined Patent Publication 6-242599 publication
Patent documentation 2 Japanese Unexamined Patent Publication 2009-166250 publication
Patent documentation 3 Japanese Laid-Open Patent Publication 63-182326 publication
Patent documentation 4 Japanese Unexamined Patent Publication 1-250334 publication
Patent documentation 5 Japanese Unexamined Patent Publication 2000-63309 publication
Non-patent literature
Non-patent literature 1Synthetic Communications, 19,1109-17 (1989)
Summary of the invention
The problem of the present invention is, it is provided that can be by α, and β-unsaturated cyclic ketone or hydroxyl replace saturated cyclic ketone with one Step reaction industry obtains 1, the manufacture method of 1,3-tri-(hydroxy phenyl) cycloalkane.
Present inventor furthers investigate for solving above-mentioned problem, found that use as α, β-unsaturated ring as raw material 2-cycloolefin-1-the ketone of shape ketone or replace the 3-hydroxyl cycloalkane-1-ketone of saturated cyclic ketone as hydroxyl, can be by making It reacts in the presence of a catalyst with phenol, and can manufacture 1 with under the reaction condition of a step industrializing implementation, 1,3-tri-(hydroxy phenyl) cycloalkane, thus complete the present invention.
The i.e. present invention is as follows.
1. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) table The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone shown or following formula (2) represent and following formula (3) represent Phenol is reacted in the presence of a catalyst,
In formula, R1Represent hydrogen atom, alkyl, alkoxyl, aryl radical or halogen atom, R2Represent alkyl, alkoxyl, virtue Fragrant alkyl or halogen atom, m represents the integer of 0～2, has multiple R in whole ring2When replacing, R2Can the most identical also Can be different, n represents the integer of 1～9,
In formula, R1、R2, m and n and described R1、R2, m and n identical,
In formula, R3Represent alkyl, alkoxyl, aryl radical or halogen atom, when a is more than 2, R3Can the most identical also Can be different, a represents the integer of 0～4, and b represents the integer of 1 or 2, but, 1 a+b 5,
In formula, R1、R2、R3, a, b, m and n and described R1、R2、R3, a, b, m and n identical.
2. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) table The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone shown or following formula (2) represent and following formula (3) represent Phenol is reacted in the presence of a catalyst,
In formula, R1Represent hydrogen atom, the straight-chain of carbon number 1～12 or the alkyl of branched, carbon number 5～12 Cycloalkyl, the straight-chain of carbon number 1～12 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～12, carbon number The aryl radical of 6～12 or halogen atom, R2Represent straight-chain or the alkyl of branched, the carbon number 5 of carbon number 1～12 ～the cycloalkyl of 12, the straight-chain of carbon number 1～12 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～12, carbon The aryl radical of atomic number 6～12 or halogen atom, m represents the integer of 0～2, has multiple R in whole ring2When replacing, R2Can the most identical can also be different, n represents the integer of 1～9,
In formula, R1、R2, m and n and described R1、R2, m and n identical,
In formula, R3Represent the straight-chain of carbon number 1～12 or the alkyl of branched, the cycloalkyl of carbon number 5～12, The straight-chain of carbon number 1～12 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～12, carbon number 6～12 Aryl radical or halogen atom, when a is more than 2, R3Can the most identical can also be different, a represents the integer of 0～4, and b represents 1 Or the integer of 2, but, 1≤a+b≤5,
In formula, R1、R2、R3, a, b, m and n and described R1、R2、R3, a, b, m and n identical.
3. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) table The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone shown or following formula (2) represent and following formula (3) represent Phenol is reacted in the presence of a catalyst,
In formula, R1Represent hydrogen atom, the straight-chain of carbon number 1～8 or the alkyl of branched, the ring of carbon number 5～6 Alkyl, the straight-chain of carbon number 1～4 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～6, carbon number 6～ The aryl radical of 12 or halogen atom, R2Represent straight-chain or the alkyl of branched, the carbon number 5～6 of carbon number 1～8 Cycloalkyl, the straight-chain of carbon number 1～4 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～6, carbon number The aryl radical of 6～12 or halogen atom, m represents the integer of 0～2, has multiple R in whole ring2When replacing, R2Permissible The most identical can also be different, n represents the integer of 1～9,
In formula, R1、R2, m and n and described R1、R2, m and n identical,
In formula, R3Represent straight-chain or the alkyl of branched, the cycloalkyl of carbon number 5～8, the carbon of carbon number 1～8 The straight-chain of atomic number 1～8 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～6, the fragrance of carbon number 6～12 Alkyl or halogen atom, when a is more than 2, R3Can the most identical can also be different, a represents the integer of 0～4, and b represents 1 or 2 Integer, but, 1≤a+b≤5,
In formula, R1、R2、R3, a, b, m and n and described R1、R2、R3, a, b, m and n identical.
4. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) table The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone shown or following formula (2) represent and following formula (3) represent Phenol is reacted in the presence of a catalyst,
In formula, R1Represent hydrogen atom, the straight-chain of carbon number 1～4 or the alkyl of branched, carbon number 1～2 straight Chain or the alkoxyl of branched, the aryl radical of carbon number 6～12 or halogen atom, R2Represent the straight of carbon number 1～4 Chain or the alkyl of branched, the straight-chain of carbon number 1～2 or the alkoxyl of branched, the aromatic hydrocarbon of carbon number 6～12 Base or halogen atom, m represents the integer of 0～2, has multiple R in whole ring2When replacing, R2Can the most identical can also Difference, n represents the integer of 1～9,
In formula, R1、R2, m and n and described R1、R2, m and n identical,
In formula, R3Represent 1 grade or 2 grades the alkyl of carbon number 1～4, the cycloalkyl of carbon number 5～6, carbon number The straight-chain of 1～4 or the alkoxyl of branched, the aryl radical of carbon number 6～12 or halogen atom, when a is more than 2, R3 Can the most identical can also be different, a represents the integer of 0～4, and b represents the integer of 1 or 2, but, 1≤a+b≤5,
In formula, R1、R2、R3, a, b, m and n and described R1、R2、R3, a, b, m and n identical.
5. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) table The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone shown or following formula (2) represent and following formula (3) represent Phenol is reacted in the presence of a catalyst,
In formula, R1Represent hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, ring penta Base, suberyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, hexamethylene oxygen Base, phenyl, indenyl, 1-naphthyl, fluorine atom, chlorine atom, bromine atoms or atomic iodine, R2Represent methyl, ethyl, n-pro-pyl, isopropyl Base, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, suberyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tertiary fourth oxygen Base, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, indenyl, 1-naphthyl, fluorine atom, chlorine atom, bromine atoms or atomic iodine, m Represent the integer of 0～2, in whole ring, have multiple R2When replacing, R2Can the most identical can also be different, n represents 1～9 Integer,
In formula, R1、R2, m and n and described R1、R2, m and n identical,
In formula, R3Represent methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, hexamethylene Base, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, Indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine atoms or atomic iodine, when a is more than 2, R3Can the most identical also Can be different, a represents the integer of 0～4, and b represents the integer of 1 or 2, but, 1≤a+b≤5,
In formula, R1、R2、R3, a, b, m and n and described R1、R2、R3, a, b, m and n identical.
6. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that represent at formula (1) 2-cycloolefin-1-ketone and the 3-hydroxyl cycloalkane-1-ketone that represents of formula (2) in, as R2The m of substituent group number, It is 0 in the case of the carbon atom adjacent with carbonyl, is 0 or 1 in the case of other carbon atom.
7. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that represent at formula (1) The trisphenol apoplexy due to endogenous wind that represents of 2-cycloolefin-1-ketone, the 3-hydroxyl cycloalkane-1-ketone that represents of formula (2) and formula (4), n It is 2～4.
8. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that represent at formula (1) The trisphenol apoplexy due to endogenous wind that represents of 2-cycloolefin-1-ketone, the 3-hydroxyl cycloalkane-1-ketone that represents of formula (2) and formula (4), n It is 3.
9. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that formula (1) represents 2-cycloolefin-1-ketone is 2-cyclopentene-1-one, 2-cyclohexene-1-ketone, 2-cycloheptene-1-ketone, 2-cyclo-octene-1-ketone, 2-ring Nonylene-1-one, 2-cyclodecene-1-ketone, 2-ring hendecene-1-ketone, 2-cyclododecene-1-ketone, 5-methyl-2-cyclohexene-1-ketone, 5-ethyl-2-cyclohexene-1-ketone, 5-propyl group-2-cyclohexene-1-ketone, 5-butyl-2-cyclohexene-1-ketone, the 5-tert-butyl group-2-ring Hexene-1-ketone, 5-methoxyl group-2-cyclohexene-1-ketone, 5-ethyoxyl-2-cyclohexene-1-ketone, 4,4-dimethyl-2-cyclohexene- 1-ketone, 5,5-dimethyl-2-cyclohexene-1-ketone, 4,5-dimethyl-2-cyclohexene-1-ketone, 4-methyl-2-cyclohexene-1-ketone, 2-methyl-2-cyclohexene-1-ketone, 6-methyl-2-cyclohexene-1-ketone, 4-methyl-2-cyclopentene-1-one, 5-methyl-2-ring penta Alkene-1-ketone, 2-methyl-2-cyclopentene-1-one, 4,4-dimethyl-2-cyclopenten-1-one or 4,5-dimethyl-2-cyclopentenes-1- Ketone.
10. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that formula (2) represents 3-hydroxyl cycloalkane-1-ketone be 3-Hydroxycyclopentanone, 3-hydroxy-cyclohexanone, 4-methyl-3-hydroxy-cyclohexanone, 4,4-diformazan Base-3-hydroxy-cyclohexanone, 5,5-dimethyl-3-hydroxy-cyclohexanone, 4,5-dimethyl-3-hydroxy-cyclohexanone, 6-methyl-3-hydroxyl Ketohexamethylene, 5-methyl-3-hydroxy-cyclohexanone, 2-methyl-3-hydroxy-cyclohexanone, 4-methyl-3-Hydroxycyclopentanone, 5-methyl-3- Hydroxycyclopentanone, 2-methyl-3-Hydroxycyclopentanone, 4,4-dimethyl-3-Hydroxycyclopentanone or 4,5-dimethyl-3-hydroxycyclopent Ketone.
11. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that at formula (3) table The trisphenol apoplexy due to endogenous wind that the phenol shown and formula (4) represent, a is 0,1 or 2.
12. according to the manufacture method of the triphen phenols described in 1., it is characterised in that under the phenol that formula (3) represents is State the phenol that formula (5) represents,
In formula, R4Represent hydrogen atom, alkyl, alkoxyl, aryl radical or halogen atom, R5Represent hydrogen atom, alkyl, alkane Epoxide, aryl radical, halogen atom or hydroxyl, but, R4And R5It it is asynchronously tertiary alkyl.
13. according to the manufacture method of the triphen phenols described in 1., it is characterised in that under the phenol that formula (3) represents is State the phenol that formula (5) represents,
In formula, R4Represent hydrogen atom, alkyl, alkoxyl, aryl radical or halogen atom, R5Represent hydrogen atom, alkyl, alkane Epoxide, aryl radical, halogen atom or hydroxyl, but, R4And R5In one when being tertiary alkyl, another is hydrogen atom, primary alkane Base or secondary alkyl.
14. according to the manufacture method of the triphen phenols described in 2., it is characterised in that under the phenol that formula (3) represents is State the phenol that formula (5) represents,
In formula, R4Represent hydrogen atom, the straight-chain of carbon number 1～12 or the alkyl of branched, carbon number 5～12 Cycloalkyl, the straight-chain of carbon number 1～12 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～12, carbon number The aryl radical of 6～12 or halogen atom, R5Represent hydrogen atom, the straight-chain of carbon number 1～12 or the alkyl of branched, carbon The cycloalkyl of atomic number 5～12, the straight-chain of carbon number 1～12 or the alkoxyl of branched, the cycloalkanes of carbon number 5～12 Epoxide, aryl radical, halogen atom or the hydroxyl of carbon number 6～12.
15. according to the manufacture method of the triphen phenols described in 3., it is characterised in that under the phenol that formula (3) represents is State the phenol that formula (5) represents,
In formula, R4Represent hydrogen atom, the straight-chain of carbon number 1～8 or the alkyl of branched, the ring of carbon number 5～8 Alkyl, the straight-chain of carbon number 1～8 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～6, carbon number 6～ The aryl radical of 12 or halogen atom, R5Represent hydrogen atom, the straight-chain of carbon number 1～8 or the alkyl of branched, carbon atom Cycloalkyl, the straight-chain of carbon number 1～8 or the alkoxyl of branched of several 5～8, the cycloalkyloxy of carbon number 5～6, carbon Aryl radical, halogen atom or the hydroxyl of atomic number 6～12.
16. according to the manufacture method of the triphen phenols described in 4., it is characterised in that under the phenol that formula (3) represents is State the phenol that formula (5) represents,
In formula, R4Represent hydrogen atom, 1 grade or the alkyl of carbon number 1～4 of 2 grades, the cycloalkyl of carbon number 5～6, The straight-chain of carbon number 1～4 or the alkoxyl of branched, the aryl radical of carbon number 6～12 or halogen atom, R5Represent The alkyl of carbon number 1～4 of hydrogen atom, 1 grade or 2 grades, the cycloalkyl of carbon number 5～6, the straight-chain of carbon number 1～4 Or the alkoxyl of branched, aryl radical, halogen atom or the hydroxyl of carbon number 6～12.
17. according to the manufacture method of the triphen phenols described in 5., it is characterised in that under the phenol that formula (3) represents is State the phenol that formula (5) represents,
In formula, R4Represent hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, ring penta Base, cyclohexyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, hexamethylene oxygen Base, phenyl, indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine atoms or atomic iodine, R5Represent hydrogen atom, methyl, Ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, positive propoxy, N-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, indenyl, 1-naphthyl, phenyl epoxide, fluorine are former Son, chlorine atom, bromine atoms, atomic iodine or hydroxyl.
18. according to the manufacture method of the triphen phenols described in 12., it is characterised in that in the phenol that formula (5) represents In, only R4And R5In any one be aryl radical.
19. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that formula (3) represents Phenol be phenol, catechol, orthoresol, 2,5-xylenols, 2，6-xylenol, 2,3,6-TMP, 2-ring Hexylphenol, 2-cyclopentylphenol, 2-phenylphenol, 2-isopropyl-phenol, 2-TBP, the 2-tert-butyl group-6-methylbenzene Phenol, 2-sec-butyl phenol, 2-isobutyl group phenol, 2-chlorophenol, 2-methoxyphenol.
20. according to the manufacture method of the triphen phenols described in 1., it is characterised in that the triphen phenols that formula (4) represents is The triphen phenols that following formula (6) represents,
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, alkyl, alkoxyl, fragrance Alkyl or halogen atom, R5Represent hydrogen atom, alkyl, alkoxyl, aryl radical, halogen atom or hydroxyl.
21. according to the manufacture method of the triphen phenols described in 2., it is characterised in that the triphen phenols that formula (4) represents is The triphen phenols that following formula (6) represents,
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, carbon number 1～12 straight Chain or the alkyl of branched, the cycloalkyl of carbon number 5～12, the straight-chain of carbon number 1～12 or the alcoxyl of branched Base, the cycloalkyloxy of carbon number 5～12, the aryl radical of carbon number 6～12 or halogen atom, R5Represent hydrogen atom, carbon The straight-chain of atomic number 1～12 or the alkyl of branched, the cycloalkyl of carbon number 5～12, the straight-chain of carbon number 1～12 Or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～12, aryl radical, halogen atom or the hydroxyl of carbon number 6～12 Base.
22. according to the manufacture method of the triphen phenols described in 3., it is characterised in that the triphen phenols that formula (4) represents is The triphen phenols that following formula (6) represents,
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, carbon number 1～8 straight Chain or the alkyl of branched, the cycloalkyl of carbon number 5～8, the straight-chain of carbon number 1～8 or the alkoxyl of branched, The cycloalkyloxy of carbon number 5～6, the aryl radical of carbon number 6～12 or halogen atom, R5Represent hydrogen atom, carbon atom The straight-chain of several 1～8 or the alkyl of branched, the cycloalkyl of carbon number 5～8, the straight-chain of carbon number 1～8 or side chain The alkoxyl of shape, the cycloalkyloxy of carbon number 5～6, aryl radical, halogen atom or the hydroxyl of carbon number 6～12.
23. according to the manufacture method of the triphen phenols described in 4., it is characterised in that the triphen phenols that formula (4) represents is The triphen phenols that following formula (6) represents,
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, 1 grade or the carbon atom of 2 grades Alkyl, the cycloalkyl of carbon number 5～6, the straight-chain of carbon number 1～4 or the alkoxyl of branched, the carbon atom of several 1～4 The aryl radical of several 6～12 or halogen atom, R5Represent hydrogen atom, 1 grade or the alkyl of carbon number 1～4 of 2 grades, carbon atom Cycloalkyl, the straight-chain of carbon number 1～4 or the alkoxyl of branched of several 5～6, the aryl radical of carbon number 6～12, Halogen atom or hydroxyl.
24. according to the manufacture method of the triphen phenols described in 5., it is characterised in that the triphen phenols that formula (4) represents is The triphen phenols that following formula (6) represents,
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, methyl, ethyl, n-pro-pyl, Isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, uncle Butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine Atom or atomic iodine, R5Represent hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, ring penta Base, cyclohexyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, hexamethylene oxygen Base, phenyl, indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine atoms, atomic iodine or hydroxyl.
25. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that formula (4) represents Triphen phenols be 1,1,3-tri-(4-hydroxy phenyl) Pentamethylene., 1,1,3-tri-(4-hydroxy phenyl) hexamethylene, 1,1,3-tri-(3- Methyl-4-hydroxy phenyl) hexamethylene, 1,1,3-tri-(3,5-dimethyl-4-hydroxy phenyl) hexamethylene, 1,1,3-tri-(3,4-bis- Hydroxy phenyl) hexamethylene, 1,1,3-tri-(3-methyl-4-hydroxy phenyl) Pentamethylene., 1,1,3-tri-(3,5-dimethyl-4-hydroxyls Phenyl) Pentamethylene., 1,1,3-tri-(3-phenyl-4-hydroxy phenyl) Pentamethylene., 1,1,3-tri-(3,4-dihydroxy phenyl) Pentamethylene., 1,1,3-tri-(3-cyclohexyl-4-hydroxy phenyl) cycloheptane, 1,1,3-tri-(3-cyclohexyl-4-hydroxy phenyl) hexamethylene, 1,1, 3-tri-(3-phenyl-4-hydroxy phenyl) hexamethylene, 1,1,3-tri-(3-tert-butyl-hydroxy phenyl) hexamethylene, 1,1,3-tri-(4- Hydroxy phenyl)-4-hexahydrotoluene, 1, double (4-hydroxy phenyl)-1-(2-hydroxy phenyl) hexamethylene of 3-, 1, double (the 4-hydroxyl of 3- Phenyl)-1-(2-hydroxy phenyl) cycloheptane.
26. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that relative to formula (1) the 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented or formula (2) represent, the benzene that formula (3) is represented Phenols uses in the scope of 3～50 mol times.
27. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that as catalyst, Use acidic catalyst.
28. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that as catalyst, Use bronsted acid catalyst or lewis acid catalyst.
29. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that as catalyst, Use hydrogen chloride gas, hydrochloric acid, sulphuric acid, phosphoric acid, anhydrous slufuric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, Aluminum chloride, iron chloride, phosphotungstic acid, silico-tungstic acid or cation exchange resin.
30. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that relative to formula (1) the 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented or formula (2) represent, uses as catalyst The hydrochloric acid of 0.1～3 mol times.
31. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that relative to formula (1) the 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented or formula (2) represent, uses as catalyst The hydrochloric acid of 0.2～1.0 mol times.
32. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that as co-catalysis Agent, uses compound or the macromolecular compound with sulfydryl.
33. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that as co-catalysis Agent, uses methyl mercaptan, ethanethio, n octylmercaptan, n-dodecyl mercaptan, TGA, β-mercaptopropionic acid, has mercapto The cation exchange resin of base or organic polymer siloxanes.
34. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that relative to formula (1) the 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented or formula (2) represent, uses as promoter 0.5～50 mole of % alkyl hydrosulfide.
35. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that relative to formula (1) the 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented or formula (2) represent, uses as promoter 2～30 moles of % alkyl hydrosulfides.
36. according to the manufacture method of the triphen phenols according to any one of 1.～5., it is characterised in that reaction temperature is 0 ～80 DEG C.
According to the present invention, do not use and be difficult to industrialization acquisition and/or high price and special raw material, or without being difficult to industry Changing the numerous and diverse and long reaction process implemented, replacing saturated cyclic ketone with α, β-unsaturated cyclic ketone or hydroxyl is raw material, By making it react with phenol, and can manufacture in the 1,3-of cycloalkanes hydrocarbon ring by by 1 step reaction process of ring-type ketone There is on position the triphen phenols of hydroxy phenyl.Thus, then it is the most required for by α to need not, and beta-unsaturated ketone etc. manufactures The reaction of raw ketone, the operation of purification.
And, by selecting optimum condition etc., it is possible to high yield obtains triphen phenols.
Detailed description of the invention
The manufacture method of the triphen phenols of the present invention described further below.
The feature of the manufacture method of 1,1,3-tri-(hydroxy phenyl) cycloalkane that the following formula (4) of the present invention represents exists In, make 2-cycloolefin-1-ketone that following formula (1) represents or the 3-hydroxyl cycloalkane-1-ketone that following formula (2) represents with The phenol that following formula (3) represents is reacted in the presence of a catalyst,
In formula, R1Represent hydrogen atom, alkyl, alkoxyl, aryl radical or halogen atom, R2Represent alkyl, alkoxyl, virtue Fragrant alkyl or halogen atom, m represents the integer of 0～2, has multiple R in whole ring2When replacing, R2Can the most identical also Can be different, n represents the integer of 1～9.
In formula, R1、R2, m and n and described R1、R2, m and n identical.
In formula, R3Represent alkyl, alkoxyl, aryl radical or halogen atom, when a is more than 2, R3Can the most identical also Can be different, a represents the integer of 0～4, and b represents the integer of 1 or 2, but, 1 a+b 5.
In formula, R1、R2、R3, a, b, m and n and described R1、R2、R3, a, b, m and n identical.
The 2-cyclenes that the formula (1) used as raw ketone compound used in the manufacture method of the present invention represents In the 3-hydroxyl cycloalkane-1-ketone that hydrocarbon-1-ketone and formula (2) represent, R1Represent hydrogen atom, alkyl, alkoxyl, aromatic hydrocarbon Base or halogen atom, R2Representing alkyl, alkoxyl, aryl radical or halogen atom, m represents the integer of 0～2, in whole ring There is multiple R2When replacing, R2Can the most identical can also be different.R1And R2During for alkyl, as alkyl, include, for example Carbon number is the straight-chain of 1～12 or the alkyl of branched or cycloalkyl that carbon number is 5～12.
Among these, as R1And R2Preferred alkyl, for straight-chain that carbon number is 1～8 or the alkyl of branched Or the cycloalkyl that carbon number is 5～6, as particularly preferred alkyl, for straight-chain that carbon number is 1～4 or branched Alkyl.
Specifically, include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, ring penta Base, suberyl etc..
In this kind of alkyl, in the range of the effect not damaging the present application, in its carbon atom, the most also can be in conjunction with halogen The substituent group of element atom, alkoxyl, phenyl etc., as the concrete example of the alkyl with substituent group, include, for example benzyl, methoxy Base ethyl, 3 chloropropyls etc..In addition, it is possible to do not replace.
And, R1And R2During for alkoxyl, as alkoxyl, include, for example straight-chain that carbon number is 1～12 or The alkoxyl of chain or the cycloalkyloxy that carbon number is 5～12.
Among these, as preferred alkoxyl, for straight-chain that carbon number is 1～4 or the alkoxyl of branched or Carbon number is the cycloalkyloxy of 5～6, as particularly preferred alkoxyl, for the alkoxyl that carbon number is 1～2.
Specifically, include, for example methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, Positive hexyloxy, cyclohexyloxy etc..
In this kind of alkoxyl, in the range of the effect not damaging the present application, in its carbon atom, the most also can be in conjunction with The substituent group of halogen atom, alkoxyl, phenyl etc., as the concrete example of the alkoxyl with substituent group, include, for example 2-benzene Base oxethyl, methoxy ethoxy, 2-chloroethoxy etc..In addition, it is possible to do not replace.
And, R1And R2During for aryl radical, as aryl radical, include, for example the aromatic hydrocarbon that carbon number is 6～12 Base.Specifically, include, for example phenyl, indenyl, 1-naphthyl etc..
Among these, as preferred aryl radical, for phenyl.In this kind of aryl radical, do not damaging the present application Effect in the range of, the most also can be in conjunction with the substituent group of alkyl, alkoxyl, phenyl, halogen atom etc., as having substituent group The concrete example of aryl radical, include, for example xenyl, 4-aminomethyl phenyl, 4-chlorphenyl etc..In addition, it is possible to do not replace.
And, R1And R2During for halogen atom, as halogen atom, fluorine atom, chlorine atom, bromine specifically can be enumerated former Son, atomic iodine.
In above-mentioned, as R1, preferably hydrogen atom, low alkyl group, particularly preferably hydrogen atom.
Additionally, as R2, the preferably low alkyl group of alkyl, alkoxyl, phenyl, more preferably methyl etc..
As R2Replacement number m, the carbon atom adjacent with carbonyl is preferably 0, and other carbon atom is preferably 0 or 1.M=2 Time, its carbon atom is preferably not adjacent with carbonyl, R2It is preferably alkyl.
R as whole ring2The position of substitution, in the case of for example, 2-cyclohexene-1-ketone skeleton, preferably 4 or/ And 5.
As structure looped carbon number n, from the viewpoint of reaction yield is good, preferably 2～4, the most excellent Electing cyclopentenes ring, cyclohexene ring, cycloheptene ring as, particularly preferred n is 3, the most preferably cyclohexene ring.
2-cycloolefin-1-the ketone represented as this kind of formula (1), specifically, include, for example 2-cyclopentenes-1- Ketone, 2-cyclohexene-1-ketone, 2-cycloheptene-1-ketone, 2-cyclo-octene-1-ketone, 2-cyclonoene-1-ketone, 2-cyclodecene-1-ketone, 2-ring Hendecene-1-ketone, 2-cyclododecene-1-ketone, 5-methyl-2-cyclohexene-1-ketone, 5-ethyl-2-cyclohexene-1-ketone, 5-propyl group- 2-cyclohexene-1-ketone, 5-butyl-2-cyclohexene-1-ketone, the 5-tert-butyl group-2-cyclohexene-1-ketone, 5-methoxyl group-2-cyclohexene- 1-ketone, 5-ethyoxyl-2-cyclohexene-1-ketone, 4,4-dimethyl-2-cyclohexene-1-ketone, 5,5-dimethyl-2-cyclohexene-1- Ketone, 4,5-dimethyl-2-cyclohexene-1-ketone, 4-methyl-2-cyclohexene-1-ketone, 2-methyl-2-cyclohexene-1-ketone, 6-methyl- 2-cyclohexene-1-ketone, 4-methyl-2-cyclopentene-1-one, 5-methyl-2-cyclopentene-1-one, 2-methyl-2-cyclopentene-1-one, 4,4-dimethyl-2-cyclopenten-1-ones, 4,5-dimethyl-2-cyclopenten-1-one etc..
In these, preferably 2-cyclopentene-1-one, 2-cyclohexene-1-ketone, particularly preferably 2-cyclohexene-1-ketone.
This kind of 2-cycloolefin-1-ketone such as can pass through 2-alkylidene in the presence of platinum catalyst (alkylidene) method (Japanese Patent Publication 58-42175 publication etc.) of cyclanone isomerization, depositing at acidic catalyst etc. Lower by 2-(1-hydroxy alkyl) cycloalkane-1-ketone dehydration isomerization method (Japanese Laid-Open Patent Publication 56-147740 publication etc.), The known method of the method (Japanese Unexamined Patent Publication 10-130192 publication etc.) etc. of dicarbonyl compound cyclizative condensation is easily obtained Arrive.
Additionally, the 3-hydroxyl cycloalkane-1-ketone represented as formula (2), specifically, include, for example 3-hydroxyl ring Pentanone, 3-hydroxy-cyclohexanone, 4-methyl-3-hydroxy-cyclohexanone, 4,4-dimethyl-3-hydroxy-cyclohexanone, 5,5-dimethyl-3-hydroxyl Pentylcyclohexanone, 4,5-dimethyl-3-hydroxy-cyclohexanone, 6-methyl-3-hydroxy-cyclohexanone, 5-methyl-3-hydroxy-cyclohexanone, 2-first Base-3-hydroxy-cyclohexanone, 4-methyl-3-Hydroxycyclopentanone, 5-methyl-3-Hydroxycyclopentanone, 2-methyl-3-Hydroxycyclopentanone, 4,4-dimethyl-3-Hydroxycyclopentanones, 4,5-dimethyl-3-Hydroxycyclopentanone etc..
This kind of 3-hydroxyl cycloalkane-1-ketone such as can be with making the existence at hydrogenation catalyst etc. of the multivalent hydroxyl group alkylphenol Under the known method of hydrogenated method (Japanese Unexamined Patent Publication 11-60534 publication etc.) etc. be readily derived.
In the phenol that the formula (3) of the another kind of raw material used in the manufacture method as the present invention represents, R3 During for alkyl, as alkyl, include, for example straight-chain that carbon number is 1～12 or the alkyl of branched, carbon number is 5 ～the cycloalkyl etc. of 12.
As preferred alkyl, for straight-chain that carbon number is 1～8 or the alkyl of branched or carbon number be 5～ The cycloalkyl of 8, as preferred alkyl, for straight-chain that carbon number is 1～4 or branched-chain alkyl, carbon number be 5～ The cycloalkyl of 6, as particularly preferred alkyl, is that the alkyl that carbon number is 1～4, the carbon number of 1 grade or 2 grades is 5～6 Cycloalkyl.Specifically, include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, ring penta Base, cyclohexyl etc..
Additionally, in alkyl, in the range of the effect not damaging the present application, in its carbon atom, the most also can be in conjunction with The substituent group of alkoxyl, phenyl, halogen atom etc., as the concrete example of the alkyl with substituent group, include, for example methoxyl group Ethyl, benzyl, 3-chloropropyl etc..In addition, it is possible to do not replace.
R3During for alkoxyl, as alkoxyl, include, for example straight-chain or the alkane of branched that carbon number is 1～12 Epoxide or the cycloalkyloxy that carbon number is 5～12.As preferred alkoxyl, for straight-chain that carbon number is 1～8 or The alkoxyl of chain or the cycloalkyloxy that carbon number is 5～6, as particularly preferred alkoxyl, be 1～4 for carbon number Straight-chain or branched alkoxyl.
Specifically, include, for example methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, Positive hexyloxy, cyclohexyloxy etc..Additionally, in alkoxyl, in the range of the effect not damaging the present application, its carbon atom In, the most also can be in conjunction with the substituent group of alkoxyl, phenyl, halogen atom etc., as the concrete example of the alkoxyl with substituent group, Include, for example methoxy ethoxy, 2-phenyl ethoxy, 2-chloroethoxy etc..In addition, it is possible to do not replace.
R3During for aryl radical, as aryl radical, include, for example the aryl radical that carbon number is 6～12.Specifically For, include, for example phenyl, indenyl, 1-naphthyl, phenyl epoxide (Phenyloxy) etc..
Among these, as preferred aryl radical, for phenyl.In this kind of aryl radical, do not damaging the present application Effect in the range of, the most also can be in conjunction with the substituent group of alkyl, alkoxyl, phenyl, halogen atom etc., as having substituent group The concrete example of aryl radical, include, for example 4-aminomethyl phenyl, p-methoxyphenyl, 4-chlorphenyl etc..In addition, it is possible to do not take Generation.
R3During for halogen atom, as halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be enumerated.
B represents the integer of 1 or 2, and b is preferably 1.A represents 0 or the integer of 1～4, preferably 0,1 or 2.
Alternatively there is no the phenol of substituent group in the para-position of the position of base, preferably hydroxyl, when b is 1, more preferably The phenol not having substituent group at least one in the meta of substituent group and hydroxyl is not had in the para-position of hydroxyl.
In the phenol that formula (3) represents, preferred phenol is represented by following formula (5).
In formula, R4Represent hydrogen atom, alkyl, alkoxyl, aryl radical or halogen atom, R5Represent hydrogen atom, alkyl, alkane Epoxide, aryl radical, halogen atom or hydroxyl.
In described formula (5), R4And R5During for alkyl, alkoxyl, aryl radical or halogen atom, as alkyl, alcoxyl Base, aryl radical, the concrete example of halogen atom, preference and preferred scope, with R3Identical.
Also, it is preferred that R4And R5Being asynchronously tertiary alkyl, when one is tertiary alkyl, more preferably another is hydrogen atom, primary alkane Base or secondary alkyl.
During additionally, raw material phenol apoplexy due to endogenous wind aryl radical replaces, only R4、R5In any one be preferably the virtue of phenyl etc. Fragrant alkyl.
The phenol represented as this kind of formula (3), specifically, include, for example phenol, catechol, orthoresol, 2, 5-xylenols, 2，6-xylenol, 2,3,6-TMP, 2-cyclohexylphenol, 2-cyclopentylphenol, 2-phenyl benzene Phenol, 2-isopropyl-phenol, 2-TBP, the 2-tert-butyl group-6-methylphenol, 2-sec-butyl phenol, 2-isobutyl group phenol, 2- Chlorophenol, 2-methoxyphenol etc..
Therefore, the 3-hydroxyl cycloalkanes that the 2-cycloolefin-1-ketone represented at above-mentioned formula (1) or above-mentioned formula (2) represent The above-mentioned formula (4) that the phenol that hydrocarbon-1-ketone and above-mentioned formula (3) represent is obtained by the manufacture method of the present invention represents Trisphenol apoplexy due to endogenous wind, in formula, R1、R2、R3, a, b, m and n and above-mentioned formula (1)～the R of (3)1、R2、R3, a, b, m and n identical.
Additionally, the R of 3 hydroxy phenyls3、a、b、R3The position of substitution and/or hydroxyl the position of substitution can identical can also Difference is the most identical.As preferred trisphenol compound, as shown in following formula (6).
In formula, R1、R2, m and n and above-mentioned formula (1) or the R of (2)1、R2, m and n identical, R4、R5With above-mentioned formula (5) R4、R5Identical.
The triphen represented accordingly, as the above-mentioned formula (4) of goal object of manufacture method or the above-mentioned formula (6) of the present invention Phenols, specifically, include, for example
1,1,3-tri-(4-hydroxy phenyl) Pentamethylene.
1,1,3-tri-(4-hydroxy phenyl) hexamethylene
1,1,3-tri-(3-methyl-4-hydroxy phenyl) hexamethylene
1,1,3-tri-(3,5-dimethyl-4-hydroxy phenyl) hexamethylene
1,1,3-tri-(3,4-dihydroxy phenyl) hexamethylene
1,1,3-tri-(3-methyl-4-hydroxy phenyl) Pentamethylene.
1,1,3-tri-(3,5-dimethyl-4-hydroxy phenyl) Pentamethylene.
1,1,3-tri-(3-phenyl-4-hydroxy phenyl) Pentamethylene.
1,1,3-tri-(3,4-dihydroxy phenyl) Pentamethylene.
1,1,3-tri-(3-cyclohexyl-4-hydroxy phenyl) cycloheptane
1,1,3-tri-(3-cyclohexyl-4-hydroxy phenyl) hexamethylene
1,1,3-tri-(3-phenyl-4-hydroxy phenyl) hexamethylene
1,1,3-tri-(3-tert-butyl-hydroxy phenyl) hexamethylene
1,1,3-tri-(4-hydroxy phenyl)-4-hexahydrotoluene
1,3-double (4-hydroxy phenyl)-1-(2-hydroxy phenyl) hexamethylene
1,3-double (4-hydroxy phenyl)-1-(2-hydroxy phenyl) cycloheptane etc..
In the manufacture method of the triphen phenols of the present invention, by the 2-cycloolefin-1-ketone making above-mentioned formula (1) represent Or the phenol that represents of the 3-hydroxyl cycloalkane-1-ketone that represents of above-mentioned formula (2) and above-mentioned formula (3) is in the existence of catalyst Under react, can obtain, with single step reaction operation, the triphen phenols that above-mentioned formula (4) represents.
Such as, obtain 1 by phenol and 2-cyclohexene-1-ketone or the reaction of 3-hydroxycyclohexan-1-ketone, 1,3-tri- Shown in the most following reaction equation of the reaction (1) of (4-hydroxy phenyl) hexamethylene.
When the phenol making two or more formula (3) is simultaneously or sequentially reacted, the substituent group of 3 hydroxy phenyls, the position of substitution And/or replace the different trisphenol of number and identical trisphenol is mixed and generates.
In the manufacture method of the present invention, the 2-cycloolefin-1-that the phenol represented at formula (3) and formula (1) represent When the 3-hydroxyl cycloalkane-1-ketone that ketone or formula (2) represent reacts, relative to 2-cycloolefin-1-ketone or 3-hydroxyl Cycloalkane-1-ketone, is preferably phenol in the scope of 3～50 mol times, more preferably 5～30 mol times, spy You Xuanwei not use in the range of 8～20 mol times, but be not limited to this.
In the manufacture method of the present invention, as above-mentioned catalyst, preferably acidic catalyst.But it is not limited to this.As Acidic catalyst, include, for example the gas shape of bronsted acid catalyst, lewis acid catalyst etc., the liquid and acid of solid, shaped Property catalyst.Specifically, include, for example the mineral acid of hydrogen chloride gas, hydrochloric acid, sulphuric acid, phosphoric acid, anhydrous slufuric acid etc., to first The metal halide class of the organic acid of benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid or trichloroacetic acid etc., aluminum chloride, iron chloride etc. or phosphorus The solid acid etc. of the heteropoly acid of wolframic acid or silico-tungstic acid etc. or cation exchange resin etc..In described catalyst, particularly preferably Hydrochloric acid or hydrogen chloride gas.
The usage amount of acidic catalyst is not particularly limited.Preferably usage amount is because of catalyst difference, the most different, so Cannot treat different things as the same, for example, during hydrochloric acid, relative to 2-cycloolefin-1-ketone or 3-hydroxyl cycloalkane-1-ketone, be preferably Make in the range of 0.1～3 mol times, more preferably 0.2～1.0 mol times, particularly preferably 0.3～0.6 mol times With.Now, the hydrochloric acid of the higher concentration of preferably 35% grade.
And then in the manufacture method of the present invention, for promoting reaction, promoter can be used.
Although not using promoter can react, but from the viewpoint of reaction yield and response speed, preferably yet Use promoter.
As promoter, it is however preferred to have the compound of sulfydryl or macromolecular compound, specifically, include, for example The alkyl sulfide alcohols of methyl mercaptan, ethanethio, n octylmercaptan, n-dodecyl mercaptan etc., TGA, β-mercaptopropionic acid Deng thiol carboxylic acid, the cation exchange resin with sulfydryl or organic polymer siloxanes etc..
It addition, when using methyl mercaptan, it is possible to use as sodium-salt aqueous solution.
The usage amount of promoter is not particularly limited, because reaction condition, kind are different, the most different, so can not one In Gai, but such as when using alkyl hydrosulfide, usage amount is relative to 2-cycloolefin-1-ketone or 3-hydroxyl cycloalkane-1-ketone Class, the scope of preferably 0.5～50 mole %, more preferably 2～30 moles %, particularly preferably 4～20 moles of %.
Reaction temperature is entered in the range of preferably 0～80 DEG C, more preferably 10～60 DEG C, particularly preferably 15～50 DEG C OK, in this kind of reaction condition, reaction is after all adding to raw material in reaction system, preferably complete within about 80 hours Become.
When reacting, reaction dissolvent can be used, it is possible to do not use, but owing to the fusing point of phenol is high, When raw material, catalyst are not sufficiently mixed, reaction dissolvent is preferably used.
When using reaction dissolvent, as long as not damaging in the range of the application effect, kind and the addition to solvent It is not particularly limited, as preferred reaction dissolvent, specifically, include, for example water, methanol, ethanol, 1-propanol or 2-propanol Deng lower aliphatic alcohols, toluene, the arene of dimethylbenzene etc., oxolane, the ethers of dioxolane etc., hexane, The saturated fat hydro carbons of heptane, hexamethylene etc. or their mixed solvent.Reaction dissolvent is relative to 2-cycloolefin-1-ketone or 3- Hydroxyl cycloalkane-1-ketone, is preferably and uses in the range of 0.1～20 mol times.
When reacting, the charging method of reaction raw materials, reaction method are not particularly limited, can be according to common biphenol Class, triphen phenols reaction used in method carry out.Such as, it is possible to by raw material, catalyst and as required by co-catalysis Agent, reaction dissolvent together load reaction vessel, then, are warming up under reaction temperature, stirring carry out instead in inert gas atmosphere Should.Or can also be in charging feedstock phenol, acidic catalyst and the reaction appearance loading promoter, reaction dissolvent as required In device, in inert gas atmosphere, at the reaction temperatures, 2-cycloolefin-1-ketone or the 3-hydroxyl ring of raw ketone are added successively Alkane-1-ketone or these raw ketones and phenol, the mixed liquor of solvent.From the viewpoint of reaction yield, preferably the latter Method.
Specifically, include, for example following method, reaction vessel loads the phenol of ormal weight, acidic catalyst And load promoter, reaction dissolvent as required, stir under nitrogen flowing, while being warming up to the reaction temperature of regulation After, add 2-cycloolefin-1-ketone or 3-hydroxyl cycloalkane-1-ketone the most successively.
In the manufacture method of the present invention, when reacting, use 3-hydroxyl cycloalkane-1-ketone as raw ketone Time, though the details of its reaction does not understands, but because 3-hydroxycyclohexan-1-ketone generates 2-cyclohexene-1-ketone in presence of an acid, So, it is possible to think in the reaction, have by 2-cycloolefin-1-ketone generate 1,1,3-tri-(hydroxy phenyl) cycloalkane can Can property.
After reaction terminating, it is separately separated from obtained reaction terminating liquid or mesh in the manufacture method of the purification present invention Thing time, applicable known to be separately separated or purification process.Such as, in reaction terminating liquid add sodium hydrate aqueous solution, The alkaline aqueous solution of aqueous ammonium etc., to neutralize acidic catalyst.Then, can add as required be separated from water aromatic hydrocarbon, The solvent of aliphatic ketone etc., carries out cooling down by the oil reservoir being separated off obtained by water layer and crystallization or after precipitating, passes through Filter and obtain crude crystals or the solid of goal object.
In addition, it is possible to the oil reservoir obtained being separated off described water layer adds water after stirring washing the most again, The operation being separated off water layer is carried out 1 time or is repeated several times carry out, carry out cooling down by obtained oil reservoir and crystallization or Precipitate, obtained crude crystals or the solid of goal object by filtration.
Also the oil reservoir that can be separated off described water layer and obtain carry out distilling and be distilled off not with solvent reaction After phenol, its residue is dissolved in suitable solvent, carries out cooling down by obtained solution and crystallization or sink Filter behind shallow lake, additionally, when goal object is difficult to crystallization, also obtained residue after distillation can be cooled down and obtain Rough thing.
Also dependent on obtained triphen phenols, reaction condition, it is being neutralized by described alkaline aqueous solution and is terminating After solution in, add suitable solvent and carry out crystallization or precipitation.
In the present invention, in order to obtain highly purified triphen phenols from described crude crystals, solid or rough thing, can use Known purification process.Such as the triphen phenols obtained by described method can be dissolved in the aromatic hydrocarbon solvent of toluene etc., methanol Deng alcoholic solvent, acetone, methyl iso-butyl ketone (MIBK) etc. aliphatic ketone solvent in, directly carry out cooling down and carrying out recrystallization or add lean After solvent, carried out cooling down and carrying out recrystallization, leach separated out crystallization, and obtain the high sterling of triphen phenols.
In above-mentioned partial crystallization operation, because becoming the difference of the triphen phenols of target, the most available the most molten with used Agent, the adduct crystallization (additive compound crystallization) of raw material phenols.
In the manufacture method of the present invention, the trisphenol apoplexy due to endogenous wind sometimes generated in the structure because of raw ketone has asymmetric Carbon atom, now, triphen phenols generally obtains with the form of raceme mixture.Additionally, from obtained racemic modification Mixture trisphenol apoplexy due to endogenous wind uses the known methods such as optically active column separation to separate, the mapping of available triphen phenols Body, diastereomer.
Hereinafter, specifically describe the present invention by embodiment, but the present invention is not limited only to following example.
Embodiment
Embodiment 1 [synthesis of 1,1,3-tri-(4-hydroxy phenyl) Pentamethylene .]
22g phenol, 1.3g 35% hydrochloric acid and 0.1g lauryl mercaptan are loaded in test tube, is warming up under nitrogen atmosphere After 40 DEG C, add 2g 2-cyclopentene-1-one, add after terminating, stir 50 hours at 40 DEG C.
Result reaction terminating liquid high performance liquid chromatography being analyzed, the composition value of goal object is (except area percentage Beyond rate/phenol) it is 15%.It addition, the yield calculated by this value of composition is 20 moles of % (relative to 2-cyclopentene-1-ones).
In reaction terminating liquid, add sodium hydrate aqueous solution be neutralized, to remove water layer.Oil reservoir adds water and carries out After washing, the oil reservoir obtained removing water layer, by distillation and concentration, is prepared from residual liquid by liquid chromatography (preparative) purity is the goal object of 87.6% (high performance liquid chromatography).Passed through NMR and liquid chromatography-mass spectrography The result that method is analyzed, the 1 of thing, 1,3-tri-(4-hydroxy phenyl) Pentamethylene. for the purpose of can confirm that out.
Molecular weight (LC/MS): 345 (M-H)-
1H NMR (400MHz) measures (solvent: DMSO-d6): with reference to table 1
The mensuration of purity and computational methods
By high effective liquid chromatography for measuring, by area percentage method (whole peaks that goal object peak area ratio is detected The ratio of the gross area) calculate.Example 2 below～embodiment 6 are obtained the most equally.
Table 1
1H-NMR (400MHz) qualification result (internal standard: tetramethylsilane)
Ownership Shift value (ppm) Signal Proton number
C～f 1.63～2.94 m 7
A, b 6.61～7.17 d×6 12
g 9.09～9.14 s 3
Embodiment 2 [synthesis of 1,1,3-tri-(4-hydroxy phenyl) hexamethylene]
20g phenol, 2g 35% hydrochloric acid and 0.1g lauryl mercaptan are loaded in test tube, is warming up to 40 under nitrogen atmosphere After DEG C, adding 2g 2-cyclohexene-1-ketone 2g, add after terminating, at 40 DEG C, stirring is reacted for 30 hours.By reaction terminating liquid The result being analyzed by high performance liquid chromatography, the composition value of 1,1,3-tri-(4-hydroxy phenyl) hexamethylene is (except area percentage Beyond rate/phenol) it is 68%.It addition, the yield calculated by this value of composition is 77% (relative to 2-cyclohexene-1-ketone).
Embodiment 3 [synthesis of 1,1,3-tri-(4-hydroxy phenyl) hexamethylene]
1412g phenol, 78.2g 35% hydrochloric acid, 15.2g lauryl mercaptan, 144g methanol are loaded the four of 3 liters of capacity In mouth flask, under nitrogen atmosphere liquid temperature is maintained at 30～35 DEG C, is simultaneously added dropwise 144g 2-cyclohexene-1-ketone 10 hours, dropping After end, stir 46 hours at 30 DEG C.
After reaction terminating, add sodium hydrate aqueous solution and be neutralized, then heat up and distillation for removing methanol.Then, exist The oil reservoir being separated off water layer and obtain adds methyl iso-butyl ketone (MIBK) and water is stirred and washes, with separate aqueous layer.Subtracting Pressure, distillate from obtained oil reservoir and remove not with the phenol of methyl-isobutyl reactive ketone.Toluene will be added in residue And the crystallization separated out at room temperature leaches, it is dried and obtains 1, the crude crystals (purity of 1,3-tri-(4-hydroxy phenyl) hexamethylene 95%, high performance liquid chromatography).
This crude crystals is dissolved in methyl iso-butyl ketone (MIBK), adds water after washing, separate aqueous layer.By obtained oil After layer concentrates, the crystallization separated out adding toluene in residue at room temperature leaches, and is dried and obtains 223.2g 1, and 1,3-tri- (4-hydroxy phenyl) hexamethylene (purity 99.4%, high performance liquid chromatography).
Yield: 42% (relative to the yield of 2-cyclohexene-1-ketone)
Fusing point: 202 DEG C (differential scanning calorimetry)
Molecular weight: 359 (M-H)-(LC/MS)
1H NMR (400MHz) measures (solvent: DMSO-d6): with reference to table 2
Table 2
1H-NMR (400MHz) qualification result (internal standard: tetramethylsilane)
Ownership Shift value (ppm) Signal Proton number
C～g 1.38～2.67 m 9
A, b 6.61～7.21 d×6 12
h 9.4 s 3
Embodiment 4 [synthesis of 1,1,3-tri-(4-hydroxy phenyl) hexamethylene]
41.6g phenol, 3.2g 35% hydrochloric acid and 0.5g lauryl mercaptan are loaded in 200ml four-hole boiling flask, at nitrogen After being warming up to 40 DEG C under atmosphere, dropping 10.7g 3-hydroxycyclohexan-1-ketone 3 hours, after completion of dropwise addition, stirs 79 hours at 40 DEG C React.The result that reaction terminating liquid high performance liquid chromatography is analyzed, 1,1,3-tri-(4-hydroxy phenyl) hexamethylene The composition value (in addition to area percentage/phenol) of alkane is 61%.It addition, the yield calculated by this value of composition is 59% (relatively In 3-hydroxycyclohexan-1-ketone).
After carrying out post processing by method similarly to Example 1, it is analyzed by NMR and LC/MS As a result, the 1 of thing, 1,3-tri-(4-hydroxy phenyl) hexamethylene for the purpose of can confirm that out.
Embodiment 5 [synthesis of 1,1,3-tri-(3-methyl-4-hydroxy phenyl) hexamethylene]
1513.4g orthoresol, 73g 35% hydrochloric acid, 14.2g lauryl mercaptan, 134.4g methanol are loaded 3 liters of capacity Four-hole boiling flask in, under nitrogen atmosphere liquid temperature is maintained at 30～32 DEG C, while dropping 134.5g 2-cyclohexene-1-ketone 3.5 hour.After completion of dropwise addition, stir 22 hours at 30～32 DEG C.After reaction terminating, during addition sodium hydrate aqueous solution is carried out With, then heat up and distillation for removing methanol.Then, in the oil reservoir being separated off water layer and obtain add methyl iso-butyl ketone (MIBK) and Water is stirred and washes, and is separated off water layer.Under reduced pressure, distillate from obtained oil reservoir and remove not with methyl tert-butyl The orthoresol of base reactive ketone.
After residue being dissolved in 1-capryl alcohol, add hexamethylene and carry out crystallization, the additive compound knot that will be separated out Crystalline substance at room temperature leaches, and is dried and obtains the 522.5g goal object 1 as white additive compound crystallization, 1,3-tri-(3-methyl- 4-hydroxy phenyl) hexamethylene.The result that obtained additive compound crystallization gas chromatography is analyzed, combine additively Quantity of solvent in thing crystallization is 16 weight %, result additive compound crystallization high performance liquid chromatography being analyzed, 1, The purity of 1,3-tri-(3-methyl-4-hydroxy phenyl) hexamethylene is 99.2% (in addition to solvent composition).
Yield: 77.9% (relative to the yield of 2-cyclohexene-1-ketone)
Molecular weight: 401 (M-H)-(LC/MS)
Fusing point: fail to confirm (differential scanning calorimetry)
1H NMR (400MHz) measures (solvent: CDCl3): with reference to table 3
Table 3
1H-NMR (400MHz) qualification result (internal standard: tetramethylsilane)
Embodiment 6 [synthesis of 1,1,3-tri-(3-phenyl-4-hydroxy phenyl) hexamethylene]
By 177g 2-phenylphenol, 0.5g lauryl mercaptan, 17.7g methanol load 1 liter of capacity four-hole boiling flask in, After under nitrogen atmosphere liquid temperature being warming up to 42 DEG C, with hydrogen chloride gas winding-up to saturated in system.Interior temperature is maintained 39～ 41 DEG C, dropping 10.1g 2-cyclohexene-1-ketone 2 hours the most wherein, after completion of dropwise addition, hydrogen chloride gas of jetting, one While stir 25 hours at 39～41 DEG C.After reaction terminating, add sodium hydrate aqueous solution be neutralized, then add toluene with It is separated off water layer.Then, add water and stir and wash, under reduced pressure, the oil reservoir obtained by separate aqueous layer distillates and removes The 2-phenylphenol not reacted with toluene, obtains 93.6g 1,1, the 3-tri-(3-that purity is 77.0% (high performance liquid chromatography) Phenyl-4-hydroxy phenyl) hexamethylene.And then be purified with preparative liquid chromatography, obtaining purity is 97.2% (efficient liquid phase Chromatography) 1,1,3-tri-(3-phenyl-4-hydroxy phenyl) hexamethylene.
Molecular weight: 587 (M-H)-(LC/MS)
1H NMR (400MHz) measures (solvent: DMSO d6): with reference to table 4
Table 4
1H-NMR (400MHz) qualification result (internal standard: tetramethylsilane)
Ownership Shift value (ppm) Signal Proton number
G～k 1.53～2.83 m 9
A, a ', a " 6.77～6.96 d×3 3
B～f, b '～f ', b "～f " 7.03～7.56 m 21
1,1 ', 1 " 9.25～9.40 s×3 3
Comparative example 1 [phenol and the reaction of 4-hexene-3-one]
19g phenol, 1.0g 35% hydrochloric acid and 0.1g lauryl mercaptan are loaded in test tube, after being warming up to 35 DEG C, add 2g 4-hexene-3-one, adds after terminating, stirs 42 hours at 35 DEG C.Reactant liquor is analyzed similarly to Example 1, but not Can confirm that out the generation of trisphenol.

Claims (25)

1. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) represent The phenol that the 3-hydroxyl cycloalkane-1-ketone that 2-cycloolefin-1-ketone or following formula (2) represent and following formula (3) represent Class is reacted in the presence of acidic catalyst,
In formula, R1Representing hydrogen atom, m represents that 0, n represent the integer of 2 or 3,
In formula, R1, m and n and described R1, m and n identical,
In formula, R3Represent straight-chain or the alkyl of branched, the cycloalkyl of carbon number 5～8, the carbon atom of carbon number 1～8 The straight-chain of several 1～8 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～6, the aryl radical of carbon number 6～12 Or halogen atom, when a is more than 2, R3Can the most identical can also be different, a represents the integer of 0～4, b represent 1 or 2 whole Number, but, 1≤a+b≤5,
In formula, R1、R3, a, b, m and n and described R1、R3, a, b, m and n identical.
2. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) represent The phenol that the 3-hydroxyl cycloalkane-1-ketone that 2-cycloolefin-1-ketone or following formula (2) represent and following formula (3) represent Class is reacted in the presence of acidic catalyst,
In formula, R1Representing hydrogen atom, m represents that 0, n represent the integer of 2 or 3,
In formula, R1, m and n and described R1, m and n identical,
In formula, R3Represent 1 grade or 2 grades the alkyl of carbon number 1～4, the cycloalkyl of carbon number 5～6, carbon number 1～4 Straight-chain or the alkoxyl of branched, the aryl radical of carbon number 6～12 or halogen atom, when a is more than 2, R3Permissible The most identical can also be different, a represents the integer of 0～4, and b represents the integer of 1 or 2, but, 1≤a+b≤5,
In formula, R1、R3, a, b, m and n and described R1、R3, a, b, m and n identical.
3. the manufacture method of the triphen phenols that a following formula (4) represents, it is characterised in that make following formula (1) represent The phenol that the 3-hydroxyl cycloalkane-1-ketone that 2-cycloolefin-1-ketone or following formula (2) represent and following formula (3) represent Class is reacted in the presence of acidic catalyst,
In formula, R1Representing hydrogen atom, m represents that 0, n represent the integer of 2 or 3,
In formula, R1, m and n and described R1, m and n identical,
In formula, R3Represent methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxy Base, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, indenyl, 1- Naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine atoms or atomic iodine, when a is more than 2, R3Can the most identical can not also With, a represents the integer of 0～4, and b represents the integer of 1 or 2, but, 1≤a+b≤5,
In formula, R1、R3, a, b, m and n and described R1、R3, a, b, m and n identical.
4. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that logical 2-cycloolefin-1-the ketone that formula (1) represents is 2-cyclopentene-1-one or 2-cyclohexene-1-ketone.
5. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that logical The 3-hydroxyl cycloalkane-1-ketone that formula (2) represents is 3-Hydroxycyclopentanone or 3-hydroxy-cyclohexanone.
6. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that Phenol that formula (3) represents and the trisphenol apoplexy due to endogenous wind that formula (4) represents, a is 0,1 or 2.
The manufacture method of triphen phenols the most according to claim 1, it is characterised in that the phenol that formula (3) represents is The phenol that following formula (5) represents,
In formula, R4Represent hydrogen atom, the straight-chain of carbon number 1～8 or the alkyl of branched, the cycloalkyl of carbon number 5～8, The straight-chain of carbon number 1～8 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～6, the virtue of carbon number 6～12 Fragrant alkyl or halogen atom, R5Represent hydrogen atom, the straight-chain of carbon number 1～8 or the alkyl of branched, carbon number 5～8 Cycloalkyl, the straight-chain of carbon number 1～8 or the alkoxyl of branched, the cycloalkyloxy of carbon number 5～6, carbon number Aryl radical, halogen atom or the hydroxyl of 6～12, but, R4And R5In one when being tertiary alkyl, another be hydrogen atom, primary Alkyl or secondary alkyl.
The manufacture method of triphen phenols the most according to claim 2, it is characterised in that the phenol that formula (3) represents is The phenol that following formula (5) represents,
In formula, R4Represent hydrogen atom, 1 grade or the alkyl of carbon number 1～4 of 2 grades, the cycloalkyl of carbon number 5～6, carbon atom The straight-chain of several 1～4 or the alkoxyl of branched, the aryl radical of carbon number 6～12 or halogen atom, R5Represent that hydrogen is former Son, 1 grade or the alkyl of carbon number 1～4 of 2 grades, the cycloalkyl of carbon number 5～6, the straight-chain of carbon number 1～4 or The alkoxyl of chain, aryl radical, halogen atom or the hydroxyl of carbon number 6～12.
The manufacture method of triphen phenols the most according to claim 3, it is characterised in that the phenol that formula (3) represents is The phenol that following formula (5) represents,
In formula, R4Represent hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, hexamethylene Base, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, Indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine atoms or atomic iodine, R5Represent hydrogen atom, methyl, ethyl, positive third Base, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, Tert-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, Bromine atoms, atomic iodine or hydroxyl.
The manufacture method of triphen phenols the most according to claim 8, it is characterised in that in the phenol that formula (5) represents In, only R4And R5In the aryl radical that any one is carbon number 6～12.
11. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that logical The phenol that formula (3) represents be phenol, catechol, orthoresol, 2,5-xylenols, 2，6-xylenol, 2,3,6-trimethyls Phenol, 2-cyclohexylphenol, 2-cyclopentylphenol, 2-phenylphenol, 2-isopropyl-phenol, 2-TBP, the 2-tert-butyl group- 6-methylphenol, 2-sec-butyl phenol, 2-chlorophenol, 2-methoxyphenol.
The manufacture method of 12. triphen phenols according to claim 1, it is characterised in that the triphen phenols that formula (4) represents The triphen phenols represented for following formula (6),
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, the straight-chain of carbon number 1～8 Or the alkyl of branched, the cycloalkyl of carbon number 5～8, the straight-chain of carbon number 1～8 or the alkoxyl of branched, carbon are former The cycloalkyloxy of subnumber 5～6, the aryl radical of carbon number 6～12 or halogen atom, R5Represent hydrogen atom, carbon number 1～ The straight-chain of 8 or the alkyl of branched, the cycloalkyl of carbon number 5～8, the straight-chain of carbon number 1～8 or the alkane of branched Epoxide, the cycloalkyloxy of carbon number 5～6, aryl radical, halogen atom or the hydroxyl of carbon number 6～12.
The manufacture method of 13. triphen phenols according to claim 2, it is characterised in that the triphen phenols that formula (4) represents The triphen phenols represented for following formula (6),
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, 1 grade or the carbon number 1 of 2 grades～ Alkyl, the cycloalkyl of carbon number 5～6, the straight-chain of carbon number 1～4 or the alkoxyl of branched of 4, carbon number 6～ The aryl radical of 12 or halogen atom, R5Represent hydrogen atom, 1 grade or the alkyl of carbon number 1～4 of 2 grades, carbon number 5～6 Cycloalkyl, the straight-chain of carbon number 1～4 or the alkoxyl of branched, the aryl radical of carbon number 6～12, halogen former Son or hydroxyl.
The manufacture method of 14. triphen phenols according to claim 3, it is characterised in that the triphen phenols that formula (4) represents The triphen phenols represented for following formula (6),
In formula, R1、R2, the R of m and n and formula (1)1、R2, m and n identical, R4Represent hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl Base, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tertiary fourth oxygen Base, n-pentyloxy, positive hexyloxy, cyclohexyloxy, phenyl, indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine atoms Or atomic iodine, R5Represent hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, ring Hexyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, cyclohexyloxy, benzene Base, indenyl, 1-naphthyl, phenyl epoxide, fluorine atom, chlorine atom, bromine atoms, atomic iodine or hydroxyl.
15. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that logical The triphen phenols that formula (4) represents be 1,1,3-tri-(4-hydroxy phenyl) Pentamethylene., 1,1,3-tri-(4-hydroxy phenyl) hexamethylene, 1, 1,3-tri-(3-methyl-4-hydroxy phenyl) hexamethylene, 1,1,3-tri-(3,5-dimethyl-4-hydroxy phenyl) hexamethylene, 1,1,3- Three (3,4-dihydroxy phenyl) hexamethylene, 1,1,3-tri-(3-methyl-4-hydroxy phenyl) Pentamethylene., 1,1,3-tri-(3,5-diformazans Base-4-hydroxy phenyl) Pentamethylene., 1,1,3-tri-(3-phenyl-4-hydroxy phenyl) Pentamethylene., 1,1,3-tri-(3,4-dihydroxy benzenes Base) Pentamethylene., 1,1,3-tri-(3-cyclohexyl-4-hydroxy phenyl) hexamethylene, 1,1,3-tri-(3-phenyl-4-hydroxy phenyl) hexamethylene Alkane, 1,1,3-tri-(3-tert-butyl-hydroxy phenyl) hexamethylene, 1, double (4-hydroxy phenyl)-1-(2-hydroxy phenyl) hexamethylene of 3- Alkane.
16. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that phase The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented for formula (1) or formula (2) represent, by formula (3) The phenol represented uses in the scope of 3～50 mol times.
17. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that make For catalyst, use bronsted acid catalyst or lewis acid catalyst.
18. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that make For catalyst, use hydrogen chloride gas, hydrochloric acid, sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, Aluminum chloride, iron chloride, phosphotungstic acid, silico-tungstic acid or cation exchange resin.
19. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that phase The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented for formula (1) or formula (2) represent, as catalyst And use the hydrochloric acid of 0.1～3 mol times.
20. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that phase The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented for formula (1) or formula (2) represent, as catalyst And use the hydrochloric acid of 0.2～1.0 mol times.
21. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that make For promoter, use compound or the macromolecular compound with sulfydryl.
22. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that make For promoter, use methyl mercaptan, ethanethio, n octylmercaptan, n-dodecyl mercaptan, TGA, β-sulfydryl third Acid, there is cation exchange resin or the organic polymer siloxanes of sulfydryl.
23. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that phase The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented for formula (1) or formula (2) represent, as co-catalysis Agent and use 0.5～50 mole of % alkyl hydrosulfide.
24. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that phase The 3-hydroxyl cycloalkane-1-ketone that the 2-cycloolefin-1-ketone represented for formula (1) or formula (2) represent, as co-catalysis Agent and use 2～30 moles of % alkyl hydrosulfides.
25. according to the manufacture method of the triphen phenols according to any one of claim 1～claim 3, it is characterised in that anti- Answering temperature is 0～80 DEG C.
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